Transition-metal

Organometallics

Peter H.M. Budzelaar

Transition metals are never on time

Late

Early
Middle

Transition-metal Organometallics

Early Transition Metals

Groups 3,4

Strongly electrophilic and oxophilic

Few redox reactions (exception: Ti)
Nearly always < 18e
Polar and very reactive M-C bonds
(to alkyl and aryl)

Few d-electrons:
preference for "hard" -donors (N/O/F)
weak complexation of -acceptors (olefins, phosphines)

Typical catalysis: Polymerisation

Me
M

Me
M

etc
Me

Transition-metal Organometallics

"Middle" Transition Metals

Groups 5-7

Many accessible oxidation states

Mostly 18e
Ligands strongly bound
Strong, not very reactive M-C bonds
Preference for -donor/-acceptor combinations (CO!)
Typical catalysis: Alkene and alkyne metathesis

CH2

CH2

M CH2

CH2
M
CH2
CH2

M CH2
CH2

CH2

Transition-metal Organometallics

Late Transition Metals

Groups 8-10 (and 11)

Many accessible oxidation states

Mostly 18e or 16e
16e common for square-planar complexes

Easy ligand association/dissociation

Weak, not very reactive M-C bonds
Even weaker, reactive M-O/M-N bonds
Preference for -donor/weak -acceptor ligands (phosphines)
Typical catalysis: Hydroformylation
H

CO

CO

O
H

M
H

H2

M
H

H2
Transition-metal Organometallics

Front- and Back-benchers

1st row
2nd row
3rd row

Transition-metal Organometallics

Going down...
1st row:
often unpaired electrons
different spin states (HS/LS) accessible
"highest possible" oxidation states not very stable
MnO4- is a strong oxidant

2nd/3rd row:
nearly always "closed shell"
virtually same atomic radii (except Y/La)
highest oxidation states fairly stable
ReO4- is hardly oxidizing

2nd row often more reactive than 3rd

Transition-metal Organometallics

M-H and M-C -bonds

M H

Hydride

M C

Alkyl

M C

Vinyl (alkenyl)

M C C

Acetylide (alkynyl)

Aryl

Transition-metal Organometallics

Synthesis of metal alkyls

Metathesis
TiCl4 + 4 BzMgCl

TiBz4 + 4 MgCl2
(Bz = benzyl, C6H5CH2)

Electrophilic attack on metal

Mn(CO)5

MeI

Insertion

MeMn(CO)5

Ar

Ar

N
N

Co H
N

Co Et
N

Ar

C2H4

Ar
Transition-metal Organometallics

Synthesis of metal alkyls

Oxidative addition
often starts with electrophilic attack

Me
O

O
L MeI
Rh
O
L

O
Rh

L
L

L = P(OPh)3

I
L
O
I
Rh
O
Me
L

L = PPh3

10

Transition-metal Organometallics

Decomposition of metal alkyls

Dominant: -hydrogen elimination
M

M
H

M
H
Alternatives:
homolysis
//-eliminations
reductive elimination (especially with H or another alkyl)
ligand metallation

11

Transition-metal Organometallics

How to prevent -hydrogen elimination ?

No -hydrogen
CH3, CH2CMe3, CH2SiMe3, CH2Ph

No empty site cis to alkyl

Et

Co

N
O

N
H

O
OH2

Product of elimination unstable

?

12

Transition-metal Organometallics

How to prevent -hydrogen elimination ?

Planar transition state inaccessible

H

H
L2Pt

L2Pt H

L2Pt

???

even for 5-membered metallacycles -elimination is difficult !

(basis of selective ethene trimerization)

13

Transition-metal Organometallics

Reactions of metal alkyls

Insertion, of both polar and non-polar C=X bonds:

olefins, acetylenes, allenes, dienes
(ketones etc)
CO, isocyanides

14

Reductive elimination

Transition-metal Organometallics

Synthesis of metal hydrides

Metathesis
WCl6 + LiBEt3H + PR3

-elimination

WH6(PR3)3

M
H

Protonation / oxidative addition

H
LnM

HX

LnM
X
+

LnM H X-

15

LnM

H2

H
LnM

LnM H2
H

Transition-metal Organometallics

Structure of WH6(PiPr2Ph)3

16

Transition-metal Organometallics

Synthesis of metal hydrides

Hydrogenolysis
Ar

Ar

N
N

Co Et
N

17

N
H2

Co H
N

Transition-metal Organometallics

Reactivity of metal hydrides

"Hydride is the smallest alkyl"

Can react as H+ or H HCo(CO)4 nearly as acidic as H2SO4

Cp2ScH gives H2 with acids, alcohols, ...

Insertion reactions
CO insertion rare (endothermic!)

18

Transition-metal Organometallics

Metal aryls
Usually much more stable than alkyls
H
H
M
M +

???

Synthesis:
Metathesis
Oxidative addition
Reaction/decomposition:
Reductive elimination

19

Transition-metal Organometallics

The other ligands...

Common ligands for transition metals:
ligands, CO, phosphines
CO

PR3

General characteristic: -donating, -accepting, "soft"

20

Transition-metal Organometallics

 ligands, CO, phosphines

-donor character:
phosphines > alkenes, CO
-acceptor character:
CO > alkenes > phosphines
Depends strongly on the substituents on P, C=C !

21

Transition-metal Organometallics

Donor and acceptor orbitals

-donor
alkene

-acceptor

CO
LP

phosphine
LP

22

Transition-metal Organometallics

 ligands, CO, phosphines

CO is one of the best -acceptors (-acids)

isocyanides are stronger donors, weaker acceptors

PMe3 very weak -acceptor, good -donor

PF3 nearly as strongly -acidic as CO

C2H4 weak -acceptor

C2(CN)4 very strong -acceptor
even forms stable radical anions

23

Transition-metal Organometallics

Synthesis of CO and -ligand complexes

Stable, neutral ligands:
generate empty site(s) in presence of free ligand
reflux in
Cr(CO)6
Cr(CO)3(C6H6)
C6H6
1.13

1.37

1.417

1.410

2.223
1.841

1.913
1.141

24

2.141

1.157

Transition-metal Organometallics

Synthesis of CO and -ligand complexes

Variation:
reductive synthesis
+
CrCl3

NiSO4

25

Al/AlCl3
C6H6

S2O42CO

Cr

+ e-

Cr

Ni(CO)4

Transition-metal Organometallics

Synthesis of CO and -ligand complexes

Anionic ligands:
introduce via metathesis (Cp-), substitution
or oxidative addition (allyl)

FeCl2

CpNa

Fe

Fe(CO)5

Fe
OC
OC

26

CO

Transition-metal Organometallics

Synthesis of CO and -ligand complexes

Cl

Mn(CO)5
or h

27

Mn(CO)5

Mn(CO)4

Transition-metal Organometallics

Modification of ligands
by H+/H- addition/abstraction
+
M

H+
- H+

acid
base

M
-

28

H- H-

H- donor: NaBH4, LiBHEt3

H- abstractor: Ph3C+ BF4-

Transition-metal Organometallics

Reactivity of -ligand complexes

Ligand activated for nucleophilic attack
both internal and external

X-

C O

M C O

M
O

29

Transition-metal Organometallics

Reactivity of -ligand complexes

Change of hapticity

30

/ allyl

ring slippage

Transition-metal Organometallics

More than 18 e ?

1.47
1.40

1.51
2.33
2.45

1.95

1.15

1.22
1.99

2.97

2.30-2.32

2.46
1.40

2.35

2.32

1.41
1.41-1.44
1.40

31

Transition-metal Organometallics

 complexes
A bond as 2-electron donor for a metal.
H2 complexes (non-classical hydrides)
CO H

CO
OC
OC

Cr

CO
CO

h
H2

OC
OC

H
CO

CO

CO

Cr

C-H bonds
Usually intramolecular

N
Rh

Pt
L

Sometimes intermolecular

CO
OC
OC

Cr

CH4
CO

In "matrix"
Characterized by IR

CO

32

Transition-metal Organometallics

 complex ?

2.10

1.92

N
Rh
H
H

33

Transition-metal Organometallics

 complex ?

+
L

L
Pt
H
34

Transition-metal Organometallics

 complexes

C-Si bonds

H
Me3Si

La

THF
H

SiMe3

Me3Si Me Si Me
Me

2.63
3.22

103

35

Transition-metal Organometallics

 complexes

Si-H bonds

OC
OC

36

Mn

SiHPh2

??

etc: B-H, Sn-Cl, P-H, ..

Transition-metal Organometallics

 complexes
A complex is an (arrested) intermediate for oxidative addition:
M

XY

X
Y

X
M
Y

M(m)

M(m)

M(m+2)

n-e

(n+2)-e

(n+2)-e

Stable complexes are formed when the metal is not

-basic enough to enable completion of the addition.

37

Transition-metal Organometallics